Organo tin compounds and compositions containing same



2,715,111 ORGAN O TlN COMPOUNDS AND COMPOSITIONS CONTAKNING SAMEElli-cit L. Weinberg, Long island City, N. Y., assignor to l etal &Therrnit Corporafion, New York, N. Y., a

corporation of Newdersey No Drawing. Application December 21, 1953,Serial No. 399,627 9 Claims. (Cl. 260-454) The invention relates to apolymer containing organotin components, to the method of making thesame and to a resin containing this polymer as a stabilizer. Thisapplication is a continuation in part of application Serial No. 235,673,filed July 7, 1951, now abandoned.

An alkyd in its simplest form is a polymeric ester resulting from thereaction of a polyhydric alcohol with a polycarboxylic acid. It has beenfound in accordance with the present invention that hydrocarbontinoxides may be substituted for a reactive portion of either thepolyhydric alcohol or the poiycarboxylic acid to produce a new series ofuseful polymers in the form of alkyds containing hydrocarbontinresidues.

it has also been found in accordance with the present invention thatthese new polymers dispersed at low concentration in vinyl resins andespecially polyvinyl chloride resins, act as stabilizers in reducing toa substantial extent the breakdown of the vinyl plastic when exposed toheat or light.

In accordance with the present invention, the new compound may beprepared by reacting alkyd forming ingredients and especially apolyhydric alcohol and a polycarboxylic acid with a hydrocarbontincompound (i. e. a compound having a hydrocarbon radical connected to thetin atom through a carbon atom of said radical) preferably in the formof a hydrocarbo'ntin oxide such as a dialkyl, or diaryl or dia-ralkyltin oxide. The resulting compound will be an alkyd whose chain includestin atoms in which tin atoms are joined to oxygen of the alkyd, each ofsaid tin atoms being joined by CSn bonds to two organic groups derivedfrom the hydrocarbon tin oxide. Suitable hydrocarbon tin oxides in cludedimethyltin-, diethyltin-, diprop'ylt'in-, dibutyltin-, dihexyltin-,dilauryltin-, diphe'nyltinand dibenzyltin-oxides.

Any polyhydric alcohol may be used but it is preferred to use one havingtwo reactive hydroxyl groups such as ethylene glycol, polyethyleneglycol, monoeste'rs of trihydric alcohols or further esterified alcoholsof higher functionality.

The polycarboxylic acid may be sebacic, 'adipic, mel- .litic (acid oranhydride form), phthalic (acid or anhydride form), maleic (acid oranhydride form), fuma'ric acid and the like. In the claims herein bypolycarboxylic acid is intended this compound not only in acid form butalso in anhydride form.

In order to produce a polymeric compound having the desired physicalcharacteristics, suitable agents for retarding the length of thepolymeric chains formed or for limiting extent of polymerization andspecifically a-monocarboxylic acid or a monohydric alcohol may be added.The monocarboxylic acid may for example be a fatty acid such as stearicacid or may be an unsaturated acid such as oleic or linoleic acid. Themonohydric alcohol which may be used as a modifying agent may be of anysuitable type, as for example butyl alcohol.

Some change in the physical characteristics of the polymeric compound ofthe present invention may be obtained by using a partially esterifiedpolyhydric alcohol instead of an unreacted 'polyhydric alcohol as one ofthe alkyd forming ingredients.

The resulting polymeric compounds are viscous liquids atent w ICC or'pastes, whitish and light yellow to amber in color and are linear orcross-linked according to the functional characteristics of thereactants. These products may contain incompletely reacted ingredients;reaction, with consequent increase in degree of polymerization,continues when they are employed as resin stabilizers.

The following examples illustrate certain ways in which the principle ofthe invention has been applied, but is not to be construed as limitingthe broader aspects of the invention.

EXAMPLE 1 Seventy-five (75) grams (.2 mol) of glyceryl monoricinoleatewere reacted with 25 grams (.1 mol) of dibutyltin oxide and grams (.1mol) of phthalic anhydride. These reactants were heated in an openbeaker until all the material was compatible. The temperature necessaryto reach this condition was 160 to 170 C. and the heating time was 15minutes. The resulting product was amber in color and viscous in nature.

It should be noted that in the method of Example 1, the phthalicanhydride and the dibutyltin oxide are permitted to react with thereactive hydroxyl groups in the glyceryl monoricinoleate. Since thereare three hydroxyl groups in the glyceryl monoricinoleate, it istri-functional. The dibutyltin oxide and the acid anhydride arebifunctional. Thus a cross-linked polymer results. As a general rule,the cross-linked polymer may be evidenced by its high viscosity.

EXAMPLE 2 Sixty-eight (68) grams of ethylene glycol monoricinoleate werereacted with grams of dibutyltin oxide and grams of phthalic anhydride.The mixture was heated to C. for 15 to 20 minutes. The resulting productwas an amber liquid of lower viscosity than the product of Example 1.

Since the ethylene glycol monoricinoleate in the method of Example 2 hastwo reactive hydroxyl groups, the "resulting polymer is linear. As ageneral rule, the linear characteristic of a polymer is evidenced by itslow viscosity.

EXAMPLE 3 Sixty-eight (68) grams of ethylene glycol monoricinoleate werereacted with 25 grams of dibutyltin oxide and 20 grams of maleicanhydride at 120 C. for 15 to 20 minutes. The resulting product wasclear and somewhat viscous.

EXAMPLE 4 Seventy-five (75) grams of glyceryl monoricinoleate, 25 gramsof dibutyltin oxide and 20 grains of maleic anhy- 'dride were heatedtogether at to C. for 30 minutes. The resulting product was a clearviscous fluid.

EXAMPLE 5 Seventy-five (75) parts of glyceryl monooleate, 25 parts ofdibutyltin oxide and 20 parts of maleic anhydride were heated togetherbetween and 200 C. for about /2 hour, until a clear amber colored fluidmaterial was obtained.

EXAMPLE 6 Seventy-five (75) parts of glyceryl monostearate, 25 parts ofdibutyltin oxide and 20 parts of maleic anhydride were heated togetherbetween 180 and 200 C. for about /2 hour. The resulting product had theappearance of a whitish wax.

EXAMPLE 7 Seventy-five (75) parts of glyceryl monolaurate, 25 parts ofdibutyltin oxide and 20 parts of maleic anhydride were heated togetherbetween 180 and 200 C. for about /2 hour. The resulting product was alight semi-solid.

EXAMPLE 8 EXAMPLE 10 Seventy-five (75) parts of glycerylmonoricinoleate, 25 parts of dibutyltin oxide and 23 parts of fumaricacid were heated together between 180 and 200 C. for about one hour. Theresulting product was a yellow semisolid.

EXAMPLE 11 Seventy-five (75) parts of glyceryl monoricinoleate, 25 partsof dibutyltin oxide and 30 parts of adipic acid were reacted together ata temperature of between 180 and 200 C. for about /2 hour. The resultingproduct was a tan crystalline waxy substance.

XAMPLE 12 Maleic anhydride 39.2 grams, butyl alcohol 14.8 grams,glycerol monoricinoleate 111.5 grams, and dibutyl tin oxide 37.3 gramswere reacted according to the following schedule. The maleic anhydridewas dissolved in butyl alcohol, the glycerol monoricinoleate and thedibutyl tin oxide were then added and the mixture was heated rapidly.Total heating time was two hours and the final pot temperature was 150C. at which temperature the mixture was held for one hour. The resultingproduct had a viscosity which was considerably lower than that of thematerial prepared in Example 4.

EXAMPLE 13 Maleic anhydride 47.2 grams, dibutyl tin oxide 50 grams, 9,11linoleic acid 110 grams, ethylene glycol 63 grams were heated in a drynitrogen atmosphere to a temperature of 200 C. and held there for threehours.

EXAMPLE 14 Diphenyl tin oxide (10 pts.), glycerol monoester ofcottonseed oil (25.85 pts.), and maleic anhydride (6.9 pts.) were heatedand stirred together at 160180 C. for 15 minutes. The resulting productwas transparent, gummy and had an orange hue.

EXAMPLE 15 Diphenyl tin oxide (10 pts.), glycerol monoester of lard oil(25.85 pts.) and maleic anhydride (6.9 pts.) were heated and stirredtogether at 160-180" C. for 15 minutes. The product was transparent,hard and orange in color.

EXAMPLE 16 Dimethyl tin oxide (16.5 pts.), glycerol monoricinoleate (75pts.) and maleic anhydride pts.) were heated and stirred together at185210 C. for 15 minutes. The product was a solid.

EXAMPLE 17 Dimethyl tin oxide (16.5 pts.), glycerol monoester ofcottonseed oil (75 pts.) and maleic anhydride (20 pts.) were heated andstirred together at 160-220" C. for 30 minutes. The product was asemi-solid;

EXAMPLE 18 Diphenyl tin oxide (10 pts.), glycerol monoester ofcottonseed oil (25.85 pts.) and sebacic acid (13.8 pts.) were heated andstirred together at 160185 C. for 15 minutes. The product was a viscous,greentinted liquid.

EXAMPLE l9 Diphenyl tin oxide (10 pts.), glycerol monoricinoleate (25.85pts.) and adipic acid (10.3 pts.) were heated and stirred together atISO-160 C. for 15 minutes. A semisolid product resulted.

The tin contents of the polymer in the examples illustrated, vary fromfive to fifteen per cent by weight with the bulk of the example productshaving about 10% tin.

The polymers of the present invention may be effectively used asstabilizers in vinyl resins and especially vinyl resins containingchlorine, such as polyvinyl chloride. As already indicated, the productsof the present invention when first applied to these resins areincomplete as regards the degree of polymerization and become morecomplete when added to the resin.

The hydrocarbontin polymers may be effectively used in concentrationsvarying from 1 to 10 parts by weight to parts of the resin. Thepreferred concentration for a polymer containing 10% tin is 2 to 4 partsper 100 ing of the stabilized resin on standing at room tempera-- turefor over six months.

In accordance with specific tests, the stabilizers produced in theExamples 1-11 were incorporated respectively into a mixture of 100 partsby weight of Geon 101 (polyvinyl chloride resin produced by B. F.Goodrich Co.) and 50 parts by weight of a plasticizer (Flexol, dioctylphthalate). The weight of the stabilizer was used to provide the sameweight of combined tin as is provided by two parts of dibutyltindilaurate. This was done in order to have a means of determining therelative merits of the various compounds.

The mixture was then milled for five minutes on a two-roll differentialspeed mill heated to 320-325 F. and removed as a sheet. Portions of thesheet were then placed in a single cavity mold (6" x 6" x 40 mils)preheated to 275 F. The mold was then placed on a press and raised to320 F. under 10,000 pounds total pressure. When the mold reached 320 Fthe pressure was increased to 40,000 pounds and held until thetemperature reached 320 F. This procedure required 5 to 5% minutes. Themold and press platens were then cooled and the pressed sheet removed.

The pressed sheet was cut into 1 x 6" strips and placed to hangvertically in clips on a tray. The tray was placed in a circulating airoven held at 320 F Samples were removed after 1 hour, 2 hours, 3 hoursand 4 hours of heat aging and were rated visually. The following tableshows the result of these tests.

Table Code: 0, colorless; vsy, very slight yellow; sy, slight yellow: y,yellow; rbr, reddish brown; br, brown; bl, black; hle, black at edges.

Appearance after heat aging Stabilizer from Example No.

1 hr. 2 hrs. 3 hrs. 4 hrs.

No stabilizer rbr b1 Dibutyltin dilaurate, 2 partsllOO parts of resin yy ble bl Example 1. sy sy y rbr Example 2. sy sy y rbr Example 3- sy syy rbr Example 4- sy sy sy y Example 5 vsy sy sy 3 Example 6- vsy sy sy yExample 7 W37 sy sy y Example 8 vsy sy sy y Example 9 vsy y y rbrExample 10-. vsy sy sy 37 Example 11 vsy y y rbr The stabilizationresults obtained by the products of examples 12 and 13 are fullycomparable with the best obtained in accordance with examples 1-1l.

Stabilizers of examples 14, 15, 16 and 18 were incorporated into amixture of 100 parts by weight of Geon 101 EP, 50 parts dioctylphthalate and 2 parts of the specific stabilizer. The mixture was milledas heretofore described, cut into strips and oven-aged at 350 F. for onehour. The results were as follows:

7colorless While the invention has been described with particularreference to specific embodiments, it is to be understood that it is notto be limited thereto, but is to be construed broadly and restrictedsolely by the scope of the appended claims.

I claim:

1. A method of preparing an alkyd polymer comprising reacting together apolycarboxylic acid, a polyhydric alcohol and a hydrocarbontin oxide.

2. An alkyd polymer whose chain includes tin atoms in which tin atomsare joined to oxygen of the alkyd,

each of said tin atoms being joined by CSn bonds to two hydrocarbongroups derived from a hydrocarbontin oxide.

3. An alkyd according to claim 2 wherein a modifying agent selected fromthe class consisting of a monocarboxylic acid and a monohydric alcoholis incorporated therein during the formation of the alkyd.

4. As a composition of matter, a chlorine containing vinyl resin and astabilizing amount of the compound set forth in claim 2.

5. As a composition of matter, a chlorine containing vinyl resin and astabilizing amount of a compound set forth in claim 3.

6. An alkyd according to claim 2 wherein tin atoms are joined to oxygenof residues resulting from the removal of hydrogen from the reactivegroups of compounds selected from the class consisting of polycarboxylicacids and polyhydric alcohols.

7. An alkyd according to claim 6 wherein a modifying agent selected fromthe class consisting of a monocarboxylic acid and a monohydric alcoholis incorporated therein during the formation of the alkyd.

8. As a composition of matter, a chlorine containing vinyl resin and astabilizing amount of a compound set forth in claim 6.

9. As a composition of matter, a chlorine containing vinyl resin and astabilizing amount of a compound set forth in claim 7.

References Cited in the file of this patent FOREIGN PATENTS 588,549Great Britain May 27, 1947

2. AN ALKYD POLYMER WHOSE CHAIN INCLUDES TIN ATOMS IN WHICH TIN ATOMSARE JOINED TO OXYGEN OF THE ALKYD, EACH OF SAID TIN ATOMS ARE JOINED BYC-SN BONDS TO TWO HYDROCARBON GROUPS DERIVED FROM A HYDROCARBONTINOXIDE.
 4. AS A COMPSOITION OF MATTER, A CHLORINE CONTAINING VINYL RESINAND A STABLIZING AMOUNT OF THE COMPOUND SET FORTH IN CLAIM 2.